Process of producing an antioxidant concentrate



Paiented July is; 1950 PROCESS OI PRODUCING AN ANTIOXIDANT OONGlN'lRA'lE Loran Old Burton, Maplcwood. N. 1., ulignor to Nopco Chemical Company. Han-lac n, N. 1., a

corporation of New Jersey No Drawing. Application January 22; Serial No. 123.651.

11 claims. (on. era-sari This invention relates to the production of antioxidants and to the stabilization of oxidizable organic substancu, primarily those .of an oily or fatty nature.

, It is'well known in the art that many oxidizable organic substances, e. g. oils, fats and waxes containing fatty acid radicals, as well as soaps thereof. tend to be detrimentally affected by exposure to atmospheric conditions for prolonged periods of time. For example, many oils and fats tend 'to develop considerable rancidity and undesirable tastes and odors upon prolonged exposure to air. This instability of Oils and fats tends to be accentuated by conventional refining processes since in many cases the refining destroys or removes the natural antioxidants contained in such substances. This characteristic instability is particularly undesirable in connection with fatsoluble vitamin-containing oils, since these oils not only show the typical tendency to become rancid upon exposure to air, but also tend to lose a considerable portion of their valuable activity. Other oxidizable organic substances manifest their characteristic instabilities in different fashions, but in practically every case their instability is highly undesirable.

As a result of the instability shown by many oxidizable organic substances, many attempts have been made to increase the resistance of these substances to the action of oxidizing influences. In a few cases there has been a fair amount of success in stabilizing fatty materials against deteriorative oxidation. However, a large number of the suggested methods for producing antioxidants andstabilizing fatty materials against oxidation have not been too successful. In many cases the potency of the antioxidants obtained has been low, and as a result the stability of the fatty materials to which they were added has not been satisfactory. In some instances the antioxidants obtained have not been sumciently miscible with the fatty materials to give a stable, desirable product. In other cases the antioxidants have had rather undesirable tastes and antioxidants.

A further object of this invention is to provide improved, highly potent antioxidants which will effectively stabilize fatty materials against oxidative changes.

Another object of this invention is to' provide improved, highly potent antioxidants which will effectively prevent loss of potency in vitamin A or D containing fatty materials.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

I have discovered that the above and other objects of the invention may be achieved by 'contacting a crude vegetable oil with concentrated ammonia and subsequently fractionating the fatty material with a solvent substantially miscible with fatty materials at room temperature but only partially miscible therewith at temperatures somewhat below room temperature, and recovering a highly potent antioxidant concentrate in that portion of the solvent which is relatively immiscible with the fatty material at temperatures somewhat below room temperature. This antioxidant is very effective in stabilizing fatty materials, and particularly fatty materials containing vitamins A or D, against oxidation.

In carrying out the process of my invention, a crude vegetable oil is first treated with concentrated ammonia. Crude vegetable oils' suitable for use in the process of my invention include, among others, the crude vegetable oils contained in oil-bearing seeds and nuts such as soybeans, peanuts, corn, wheat, cottonseed, sesame, seed. rice, rye, barley, oats, coconuts, etc.

In carrying out the ammonia treatment step of the process of my invention, the crude oil may be contacted with ammonia under varying circumstances. For exampleythe crude vegetable oil may be removed from its source material and then contacted with the ammonia; the crude vegetable oil may be contacted with ammonia prior to removal from the source material, i. e. by contactingan oil-bearing vegetable meal or other vegetable material containing the desired oil with the ammonia; or a crude vegetable oil may be added to-a quantity of the same or a different type of vegetable material from which the oil was derived which vegetable material may have had none or any varying amount up to all of its original oil content previously removed therefrom, and' then contacting the crude vegetable oil in such admixture with the ammonia.

Naturally, of course, in the above procedures, in-

I I 2,515,858 UNITED STATES PATENT OFFICE atlases stable and highly potent vitamin concentrate may be produced.

When the ammonia treatment is carried out on a crude vegetable oil associated with vegetable materials, the vegetable materials are preferably ground, chopped, flaked, comminutedgir otherwise finely divided prior to the ammonia treatment. Many oil-bearing vegetable materials are commercially available in the meal form such as, for example, cottonseed meal, soybean meal, sesame meal, corn meal, corn germ meal, wheat germ meal, alfalfa leaf meal, peanut meal, rice bran, and rye, barley and other similar vegetable meals. The oil content of these vegetable materials varies considerably, of course. When treating a crude vegetable oil without removing .it from the original source material, it is usually preferred to employ a vegetable material which has a relatively high oil content; however, quite excellent results may be obtained by carrying out the process upon vegetable materials having a rather low oil content. In most cases, however, it is preferred to employ oil-bearing vegetable materials'containingat least of oil. Whenever the term oil-bearing vegetable meal is used in the specification and claims it is to be understood that the term connotes any of the oil-bearing vegetable materials as set forth in the specification. W

When the ammonia treatment is carried out upon a crude vegetable oil which has been admixed with the same or a different type of vegetable material from which the crude oil was derived, the vegetable material may still contain its original oil content, or it may have had any varying amount up to and including all of its original oil content removed. The crude vegetable oils may be obtained from any of the various oilbearing vegetable materials listed above or from other sources. Likewise the vegetable materials employed may be any of those listed above or any other suitable vegetable material. The vegetable oil added to the vegetable material may be the same oil as is obtainable from the vegetable material or it may be an entirely different vegetable oil. Since it is preferred in some cases when treating a crude vegetable oil associated with a vegetable material to treat such a vegetable material containing a fairly high percentage of oil, e. g. 40% to 50% of oil, it is desirable in some instances to increase the oil content of a vegetable material which already contains in its natural state a considerable amount of oil. Thus in some cases it may be preferred to add a sufllcient amount of a vegetable oil to an oil-bearing vegetable material containing, for example, of oil to bring, its oil content up to as high as or 50% or more. The vegetable oil which is added to a vegetable material already containing a considerable amount of oil may be the same 011 as is obtainable from the vegetable material, or it may be an entirely diflerent vegetable oil.

The concentrated ammonia which is employed in the process of my invention is preferably 28% aqueousammonia. However, other concentrated aqueous solutions of ammonia as well as gaseous ammonia or liquid ammonia may be utilized. The amount of ammonia used is relatively small as compared to the amount of vegetable oil. At least about 1% by weight of 28% aqueous ammonia as' compared to the weight of the material being treated'should be employed. Ordinarily I "prefer to employ from about 20% to about 60% of 28% aqueous ammonia based upon the weight of the material being treated. If desired, even much larger amounts of ammonia may be used, e. g. or more; however, the use of such large amounts of ammonia while not being detrimental is not particularly advantageous. When other forms of ammonia are being employed, the 1amiorilmts used are equivalent to that just set Preferably the crude vegetable oil is treated with the ammonia in the presence of a solvent for the oil. However, it is not necessary to carry out the treatment in the presence of a solvent, and in some casesut may be preferred not to do so. For example, in the event that ammonia gas is used, the process may be carried out in a closed 'fvessel under pressure of the ammonia gas. The

length'of time of contact of the crude vegetable oil with the ammonia will vary depending upon whether or not the treatment is carried out in the presence of a solvent for the oil and whether the treatment is carried out at room temperature or at elevated temperatures. Both the presence of the solvent and increased temperatures will accentuate the action of the ammonia and thus reduce the amount of time necessary for the treatment step. :When treating the crude oil in the presence of a solvent, it is preferred to heat the mixture at the reflux temperature of the solvent for ashort time, e. g. half an hour to an hour although it may be heated longer, if desired. The heating may be carried out in an inert atmosphere, e. g. in the presence of nitrogen gas, if desired.

Oil solvents which may be used in the ammonia treatment step of my process include hydrocarban and halogenated hydrocarbon solvents such as hexane, heptane, octane, ethylene dichloride. trichloroethylene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, etc., as well as solvents such as acetone, isopropanol, dia'cetone alcohol and the like. Of these many solvents I prefer to employ acetone as it appears to give the most favorable results in the process. However, any of the other solvents will give excellent results, and they, or any desired mixtures there"- of, may be used if desired.

If the process of the invention has been carried out upon a crude vegetable oil associated with a vegetable meal, or other similar vegetable material, the solvent with the crude oil dissolved therein, is separated from the vegetable meal after the ammonia treatment has been completed, and the meal is then washed with additional portions of the same oil solvent, or a different oil solvent, if desired, to completely remove the oil therefrom. If no oil solvent has been employed in the ammonia treatment step of the process, the oil containing the highly potent antloxidants may be removed from such vegetable material by washing the same with one of the oil solvents listed above. However, if desired, the treated oil-bearing vegetable material may be dried by exposure to the atmosphere, or by any other suitable means, thus removing the ammonia and the greater part of any oil solvent employed in the ammonia treatment step. The fatty material may then be removed from the treated oil-bearing vegetable material by extraction with any suitable oil solvent. Instead of removing the oil from the oil-bearing vegetable material by means of solvent extraction, other conventional means of removing the'oil from the oil-bearing vegetable material, e. g. the expeller process or the hydraulic process, may be employed to remove the oil in all the above cases from the oil-bearing vegetable material.

therein a large amount of of the process.

. 5 treated oil will have dissolved hi hly potent antioxidants. The exact nature of these antioxidants has not yet been determined. No, doubt a large percentage of these antioxidants wereorisinally present in the crude vegetable oil, and in the vegetable meal or similar vegetable material if such were employed in the process of the invention, and the effect of the ammonia treatment was to release these antioxidants with much greater emciency than has ever been done heretofore. However..it is very probable that the ammonia also reacted with certain of the original antioxidants in such a manner as to greatly increase their potency or to produce therefrom The ammonia new antioxidants of greater potency than the" original antioxidants. Furthermore, it may be that-the ammonia treatment converts certain compounds in the vegetable oil and vegetable meal which themselves have no antioxidant activity into materials which are excellent antioxidants. The most probable explanation is'that a combination of all of the above occurs. Whatever may be the true explanation, I have discovered that the treatment as outlined hereinabove produces very highly potent antioxidants.

However, sincethey are; dissolved in a relatively large amount of oil, it is desirable that they be these various solvents become partially immiscible with fatty materials will vary. In practically all cases these solvents are partially immiscible with fatty materials at temperatures of 0 C. or below. However, a few of these solvents. e. g. isopropanol. are partially immiscible with fatty materials at temperatures only slightly below room temperature, My experiments have shown that solvents falling within the above classes of compounds may be used in the practice of my invention. In additionit' will be noted that my preferred solvents possess relatively low freezing points.

In order to more fully illustrate the nature of I the solvents which I may employ, a partial list thereof is herewith given; it is to be understood. however, that this list is not intended to be complete,'.but is merely illustrative of the solvents which may be employed. Thus I have found that the following solvents maybe used: n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, n-amyl alcohol, isoamyl alcohol, secondary amyl alcohol,

concentrated by separating them from the bulk w of the oil.

If a crude vegetable oil has been treated in association with a vegetable meal or similar material, the treated oil may be separated from the solvent used to remove the oil from the treated oil-bearing vegetable material following the ammonia treatment step by simply distilling of! the solvent; however, if such oil solvent is one which is suitable for use in the solvent extraction step no such separation need be made. Instead a suilicient amount of solvent to obtain the desired ratio of solvent to oil is either added to or removed from the solution whichever may be necessary, if either.

In carrying out the separation of the antioxidants from the highly potent oil solution thereof, the oil is mixed with a, solvent which is substantially miscible with fatty materials at room temperature, i. e. 20-'25 C. and partially immiscible therewith at temperatures somewhat below room temperature, e. g. 0 C. or below. Such solvents which I have found to be suitable for use in the process of my invention fall into several well-defined classes. The following table sets forth the classes of solvents which I have found to be particularly useful in the solvent extraction step of my invention.

Table l not more than 6 carbon atoms.

4. Aliphatic ketones containing not more than 6 carbon atoms.

Solvents falling in the classes above listed are all liquid aliphatic organic compounds having the properties of being substantially miscible with fatty materials at temperatures above room temperature,

i. e. 20 to C., and partially immiscible therewith at temperatures somewhat below room temperature. The temperature at which furfuryl alcohol, allyl alcohol, 'diacetone alcohol.

p-hydroxy' ethyl acetate, methyl formate, ethyl formate, ethyl acetate, methyl acetate, isopropyl acetate, glycol diformate. glycol dlacetate, methyl levulinate, ethyl levulinate, methyl aceto acetate, ethyl aceto acetate, methyl furoate, vinyl acetate, furfural, propionaldehyde, crotonaldehyde, acetone, methyl ethyl ketone, acetonyl acetone and propylene chlorhydrin. Mixtures of these solvents may also be used. It will be noted that all these solvents belong to that class of allphatic organic compounds which have the properties of being miscible with fatty materials at temperatures above room temperature and partially immiscible therewith at temperatures somewhat below room temperature; furthermore,

' it will be noted that the majority of these solvents have relatively low freezing points.

Occasionally it may be found that certain of the solvents hereinabove mentioned may be too miscible with some of the fatty materials which may be treated by my invention to effect aseparation of antioxidants therefrom; thus, for example, acetone is too miscible with many fatty materials to accomplish the purposes of my invenvention. However, this condition may be easily corrected by diluting the solvent either with a small amount of water or with some liquid aliphatic organic solvent relatively immiscible with fatty materials. In general it may be said that the effect of diluting any of the above solvents with water will be to render the solvent more immiscible with fatty materials, so that if dimcuity is encountered in efiecting proper separation of the antioxidant extracts from the fatty materials. this difllculty may generally be overcome by the .addition of a small amount of water to the solvent. Furthermore the degree of cooling which will be required to bring about the partial immiscibility of the solvent with a fatty material will be less with such a diluted solvent as compared to the undiluted solvent.

The solvents I prefer to employ in the practice of my invention are acetone and the allphatic alcohols containing from 3 to 6 carbon atoms; of the alcohols isopropanol and diacetone alcohol have proved tube the most successful. The presence of the hydroxyl group in the alcohols seems to impart to these solvents properties which make them particularly useful for my purposes; whether this factor is due to some activating influence possessed by this group is not known.

' materials at room temperature, but only partially miscible therewith at temperatures somewhat below room temperature. The relative proportion of oil to solvent may vary widely; preferably the ratio of solvent to oil should be greater than one, and in most casesmixtures containing between about 2% and about oil are most' suitable. It is preferable to cause substantially all of the oil to dissolve in the solvent; complete solution may be readily effected by heating the mixture to a temperature substantially above room temperature. However, it is not necessary to cause the'oilto dissolve completely in the solvent, since the antioxidants may be very effectively extracted from the oil solution thereof by agitating the oil with the solvent at a temperature such that only partial solution is effected. In fact, the complete extraction step may be carried out at temperatures substantially below room temperature, if desired, in which case the solvent and the oil will at no time be completely miscible. The extraction may be carried out, if desired, in an inert gas atmosphere, e. g. in the presence of nitrogen gas. when the process cf the invention is carried out on a crude vegetable oil associated with a vegetable meal, it is'preferred to separate the oil from the vegetable meal prior to carrying out the fractionation step. However, such removal may be dispensed with, if desired, and the fractionation step may be carried out directly upon the treated oil-bearing vegetable material by contacting the fractionating solvent therewith.

The antioxidant concentrate may be recovered in any suitable manner. When operating-in accordance with the preferred method of solvent extraction, 1. e. when the oil is completely dissolved in the solvent at somewhat elevated temperatures, the recovery of the antioxidant concentrate is most conveniently accomplished by cooling the solution to a temperature sumciently below room temperature so that two layers will form, a solvent layer and an oil layer. In every case the solvent layer will contain practically all of the antioxidants. In most cases such layer formation takes place on cooling the solution to approximately 0 C. However, in some instances,

cooling of the solution just a few degrees below room temperature will bring about the desired layer formation. In such cases, of course, the solution need not be cooled to a temperature as low as 0 C. As long as the solution is cooled to a temperature where layer formation occurs, such cooling will be suflicient to effect the purposes of the invention. In most cases I prefer to cool the solution to at least 0 C. and even as low as --18 C., since such lower temperatures more effectively concentrate the antioxidants in the solvent layer. However, as pointed out above, as long as the cooling is sufllcient to cause the solution to separate into a solvent layer and an oil layer, excellent concentration of the antioxidants will be brought about. Regardless of the method by which the separation of the antioxidants from the oil is efl'ected, it will be found that they will be concentrated in that portion of the solvent which is substantially immiscible with the oil at temperatures somewhat below room temperature. If desired the extraction step may be repeated one or more times to ensure com- QJIDJBB plete recovery of the antioxidants. Also, a continuous countercurrent extraction process may be utilized, if desired, rather than using a batch process.

The solvent solution which is immiscible with,

the .oil at the low temperature may be filtered.

if desired, and then treated to remove the solvent therefrom, e. g'. by vacuum distillation. On the removal of the solvent, an antioxidant concentrate far more potent than any previously produced will be obtained. If desired, water may be added to theconcentrate to precipitate any glycerides therein or some of the sterols may be removed; however, these steps are not essential since the glycerides and sterols do not inhibitv the antioxidant properties of the concentrate. If the ammonia employed in the ammonia treatment step of the process has not already been evaporated or .distilled oil incidental to the previous steps of the process, it will be removed in the final step of the process when the extracting solvent is removed from the antioxidant concenra e.

Although the exact nature of these'antioxidants has not yet been determined, I have observed that the antioxidant concentrates have a lower iodine value than the vegetable oils from which they are derived.

My novel antioxidants may be employed for the'stabilization of all types of oxidizable organic substances, particularly those of a fatty nature. i. e. fatty oils, fats, waxes, soaps, vitamin concentrates, etc; Thus oils and fats of animal, vegetable or fish origin, such as cod liver oil, tuna liver oil, shark liver oil and other fish liver oils, as wellas vitamin concentrates or vitamin-containing fractions obtained from such oils; corn oil, cotton seed oil, soybean oil and othervegetable oils; fats such as butter, margarine, lard, hydrogenated shortenings, palm oil, etc.; soaps of higher fatty acids; and compositions containing such fatty materials as essential ingredients. e. g. food emulsions such as mayonnaise, may all be suitably stabilized in accordance with my'invention. Furthermore, substances such as sulfonated oils and other sulfonated fatty compounds, amides, mono and diglycerides and'other fatty substances which tend to become rancid upon exposure to air may be treated by my invention. The amount of the extract added to the fatty material to be stabilized may vary considerably, depending upon the activity of the extract and the degree of instability of the fatty material; I have found that oils or fats containing anywhere from about 0.1% to about 20%. preferably from about 0.5% to about 5% ofmy antioxidant extracts show striking improvements in their stability.

While my invention is primarily concerned with the stabilization of oxidizable organic substances of a fatty nature, other oxidizable organic substances, such as rubber, substances containing vitamin C, pyrethrum, essential oils and other materials known to the art may be stabilized by treatment with my novel extracts.

For a fuller understanding of the nature and objects of the invention reference may be had to the following examples which are given merely to further illustrate the invention and are not to be construed in alimiting sense.

Example I of crude vegetable oils were.

of four parts of solvent to one part of oil being employed. The solvent and the oil were contacted at room temperature, then cooled to a masseswereairdriedatroomtemperatiu'cin open trays: The'treated air-dried materials were then extracted with ethylene dichloride to remove the fatty material. These solvent extracts 5 were filtered. and the solvent removed therefrom 1 by distillation under reduced pressure. Portions of the fatty materials were then fractionated with various oi theifractionating solvents listed hereinabove'. two extractions being made in each temperature-oi 18 C. Two layers formed in case with aratio of four parts of fractionating each case at slightly below room temperature; solvent to one part of fatty material being em-. however. the mass was cooled to th lower temployedl The solvent and the fatty material were perature in order to obtain a more eflicient concontacted at room temperature and then cooled centration of the antioxidants. The solvent layto a temperature of 18C. Twolayers formed er was separated from that portion of the oil at slightly below room temperature; however, immiscible therewith, and a highly potent antiby cooling to the'lower temperature a'more eilioxidant concentrate was recovered in each case cient concentration of the antioxidants was obupon removal of the solvent from the solvent tained. The solvent layer was separated from' layer by distillation under reduced pressure. that portion or the fatty material. immiscible The relative potencies of these antioxidants 2o therewith. and a highly potent antioxidant conwere compared with the potencies of antioxicentrate was recovered in each case upon redants prepared by the processof my U. 8. Patent moval of the solvent from the solvent layer by No. 2,345,576 patented April 4, 1944 by admixing distillation under reduced pressure.

with various samples of a refined shark liver oil, To demonstrate the stabilizing action of these amounts of the various antioxidants equal to 3% antioxidants, various samples of a refined shark of the weight of each shark liver oil sample. The liver oil were "admixed with amounts of the antistability of these samples of shark liver oil was oxidants equalto 3% of the weight of each shark then determined by maintaining the samples at liver oil sample. The stability of these samples a temperature of 345 C. in contact with the was then determined as in Example I. Aconatmosphere, and measuring the percentage of trol experiment 'on' an unstabilized sample of vitamin A loss in each sample after a definite shark liver oil was also conducted. To further number of days had elapsed. A control experishow the potency of the antioxidant concenment on an unstabilized sample of refined shark trates of this invention, several samples f shark liver oil was also conducted. liver oil were stabilized by adding thereto anti- Further details and the results of the above oxidant concentrates prepared by the fractionaexperlments are given in the following table: tion of fatty materials extracted from untreated eassessment GM Mis.ol Cone Mk Solvent Usedin Per Cent AMP Vegetable Oil vemon Amgygnis Axum, g r al tionetion lnfienl d g Bdeys 14 days flldays .s m e s2 s: w 100 n 1.0 0 can 600 am 2,000 n as o 1.2 at 100 n 15.1 3.4 so ine one son 2.000 n mo 0 1.2 so

Refined Shark Liver oil containing no antioxidant concentrate has a vitamin A loss of 41.5%, alter 6 days I These examples show the use oi antioxidant concentrates prepared by the process oi my April 4, 1044.

Example II Severalsamples of oil-bearing vegetable materlals were treated with concentrated aqueous 4 B. Ifatent No. 2,345,576, patented oil-bearing vegetable materials. The stability of the vitamin A in these samples was not nearly as great as in those samples stabilized by the antioxidant concentrates oi the present invenammonia in" thepresence of acetone by mixing non.

for about one hour at a temperature of about 55f C. under .reflux conditions. The treated Further details and the results of the above experiments are given in the following table Mls i Ratl V l I i??? 1 ilned shark o o o e e Guam! v 8 Concen- Mk 01 mg C4340]; Bel-cent %9:;a' Percent Liver Oil After-- table Materfi m m. Acetone with 2 1] z gfl Fractlonfig:

Veg. at. 0) 01840]: vs at. V ation Step 5 14 27 1 a a L days days da s days Control Sample of Refined Shark Liver-Oil Containing No Antioxidant Ooneentra 57. 0 Ground Soybeans L. 1, M0 2 5I2 l2. 0 91% Iso- 6. 0 6. 8 l7. 3

1 l grqopanol. Do 2,01!) 200 2,11!) 2 5/2 14.7 3 Ace- 6.9 0.0 5.0 120 A no. 1 D04. 2,111! 11) 2M 2 5/2 14.7 01% lso- 10.8 0.0 2.6 8.6 Ground l 'lasseed mo 2 4/1 as. 4 1m 1s. 5 52. o

l, (I!) 1, 0w 2 4/1 33. 0 I A 14. 6 2 6 8. 2 l0. 1 WholeWheatGerm I, 8 5/2 9.2 In Q8 3.4 13.3 3.0 o 1,411) 1m 5m 3 5/2 9.4 n 19. 6 1.5 7.9 18. 9 OornGermMealL. 2,000 a 2/1 1.5 m as 15.5 44.1 I

Do.. 2, M 200 2, (I!) 3 2/1 7. 9 I n 22. 0 1.3 3. 1 5 0 6. 5

I These examples show the use 0! antioxidant concentrates prepared by the procem oi my U. 8. Patent No 2,345,576, patented April 4, i944.

Example m Also samples of the various crude vegetable oils V employed to increase the oil content of the relatlvely oil-free vegetable materials were fractionated, and the potency of the resulting antioxidant concentrates compared with that of the antioxidant concentrates prepared by the process of the presentinvention. In each case when an antioxidant concentrate, was added it was added in an amount equal to 3% of the weight of the oil being stabilized.

Details and results of the above experiments are given in the following table. In each case when the fatty material was extracted from the vegetable oil-vegetable meal mixture, three extractions with ethylene dichloride were made employing a ratio of one to one (mls./gms.) of solvent to vegetable oil-vegetable meal mixture.

miscible therewith at temperatures somewhat below room temperature, and separating a solvent solution containing a highly active antioxidant extract from the fatty material immiscible with the solvent at the temperature somewhat below room temperature.

4. In a process for producing an antioxidant concentrate, the steps comprising contacting a crude vegetable oil with ammonia in the presence of a solvent for fatty materials, contacting the ammonia-treated oil' with a solvent substantially miscible with fatty'materials at room temperature and only partially miscible therewith at temperatures somewhat below room temperature, and separating a solvent solution containing a highly active antioxidant extract from the oil immiscible with the solvent at the temperature somewhat below room temperature.

5. In a process for producing an antioxidant concentrate, the'steps comprising contacting an oil-bearing vegetable material with ammonia in the presence of a solvent for fatty materials, removing fatty material from the oil-bearing vegetable material, contacting the fatty material with a solvent substantially miscible with fatty materials at,room temperature and only partially Per Cent Vitamin 0 m. of Solvent Vit a in C 2 in I Per Cent m on 0 .Gms. f Cone. Am- M'ls. oi Yield Used in 1 Oil Aim veg'mma Meal vagemme "e 2. Oil 'Veg. Mgal mo Acetone Oil (gms. Fractionaf g: n! r- (28%) mm t p days days days Refined Shark Liver Oil Containing No Antioxidant Oonoentra 62. 0 Soy on L s00 0g] 8. 8 9. 5 20. 8 r 0 Jim Oil MeaL- 50 1,000 1 000 300 2.000 1.160 n 10.0 0 0 0 t me Bran an 1, 000 11000 300 2. 000 1,052 r 0 l2. 1 o 1. 2 a 4 isoybean Meal... do 1, 000 l, 000 800 1, 5M 1, 189 0 0. 2 0 0 0 Corn Germ Med l. 000 1,011] 300 1, 000 l, 170 n 9. 7 0 0 2.0

I This example shows the use of an antioxidant concentrate prepared by the procem of my U. 8. Patent No. 2,345,676, patented April 4, 1944.

Having described my invention, what I claim as new anddesire to secure by Letters Patent 1. In a process for producing an antioxidant concentrate, the steps comprising contacting a crude vegetable oil with ammonia, contacting the ammonia-treated oil with a solvent substantially miscible with fatty materials at room temperature and only partially miscible therewith at temperature'somewhatbelow room temperature, and separa'ting a solvent solution containing a highly active antioxidant extract from the oil immiscible with the solvent at the temperature somewhat below room temperature.

2. In a' process for producing an antioxidant concentrate, the steps comprising contacting an oil-bearing vegetable material with ammonia, contacting the treated material with a solvent substantially miscible with fatty materials at room temperature and only partially miscible therewith at temperatures somewhat below room temperature, and separating a solvent iolution containing a highly active antioxidant extract from the treated material and the .i'atty material therein immiscible with the solvent at the temperature somewhat below room temperature.

3. In a process for producing an antioxidant concentrate, the 'steps comprising contacting an oil-bearing vegetable material with ammonia, removing fatty material from the oily-bearing vegetable material, contacting the fatty material with a solvent substantially miscible with fatty ma- 6. In a process for producing'an antioxidant concentrate, the steps comprising contacting a crude vegetable oil with ammonia in the presence of a solvent for fatty materials, heating the mass for a short time at the reflux temperature of the solvent, contacting the ammonia-treated oil with;a solvent substantially miscible with fatty materials at room temperature and only partially miscible therewith at a temperature somewhat below room temperature, and separating a solvent solution containing a highly active antioxidant extract from the oil immiscible with the solvent at the temperature somewhat below room temperature.

T. In a process for producing an antioxidant concentrate, the steps comprising contacting an oil-bearing vegetable material with ammonia in the presence 'of a solvent for fatty materials, heating the mass for a'short time atthe reflux temperature of the .solvent, removing fatty matrrials from the oil-bearing vegetable material, contacting the fatty material with a solvent substantially miscible with fatty materials at room temperature and only partially miscible therewith at a temperature somewhat below room 7 temperature, and separating a solvent solution and separating the solvent layer containing a. highly active antioxidant extract from theoil i'lfIn a process for producing an antioxidant concentrate. the steps comprisincontactinc an ammonium hydroxide in the presence of acetone. heatin: the mass for a short time at the reflux temperature oi the acetone, removing iatty materials from the oil-bearing vegetable material by extraction with ethylene dichloride, contactin: the fatty material at a temperature above oil-bearing vegetable material with concentrated 1o room temperature with isopropanol, the ratio oi I solvent to fatty material being greater than 1. cooling the mass to a temperature somewhat below room temperature whereby layers are formed, 20

16 andJepara .the solvent layer containing the highly active antioxidant extract from the re-; mainder oi the iatty material.

' LORAN om nux'nou.

. rh'nnnucns crrm The ioliowinzreierenees are oi record in my iiie 0! this patent:

' I UNITED STAT? PATENTS Number Name Date 1,515,947 Hail Nov. 18, 192i 1,s5o,o95 Denaler "Mar. 22, 10s: 2.098.254 Mattill et al. .Nov. 9, 193'! 2,320,970 Lansing June 1, ms 2,878,852 Altschul May 22, 1945 2.396.680 Button Mar. 19, 1946 2,426,485 Buxton et al. Aug. 28, lili'l 2,426,486 Button et al. Aug. 28. 194'! 'Buxton et al. Jan. 20, 1948 

1. IN A PROCESS FOR PRODUCING AN ANTIOXIDANT CONCENTRATE, THE STEPS COMPRISING CONTACTING A CRUDE VEGETABLE OIL WITH AMMONIA, CONTACTING THE AMMONIA-TREATED OIL WITH A SOLVENT SUBSTANTIALLY MISCIBLE WITH FATTY MATERIALS AT ROOM TEMPERATURE AND ONLY PARTIALLY MISCIBLE THEREWITH AT TEMPERATURE SOMEWHAT BELOW ROOM TEMPERATURE, AND SEPARATING A SOLVENT SOLUTION CONTAINING A HIGHLY ACTIVE ANTIOXIDANT EXTRACT FROM THE OIL IMMISCIBLE WITH THE SOLVENT AT THE TEMPERATURE SOMEWHAT BELOW ROOM TEMPERATURE. 